EP2642569B1 - Membrane d'électrolyte pour piles à combustible à polymère solide, système d'électrode de membrane comprenant cette membrane d'électrolyte, et pile à combustible à polymère solide - Google Patents

Membrane d'électrolyte pour piles à combustible à polymère solide, système d'électrode de membrane comprenant cette membrane d'électrolyte, et pile à combustible à polymère solide Download PDF

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Publication number
EP2642569B1
EP2642569B1 EP11854577.1A EP11854577A EP2642569B1 EP 2642569 B1 EP2642569 B1 EP 2642569B1 EP 11854577 A EP11854577 A EP 11854577A EP 2642569 B1 EP2642569 B1 EP 2642569B1
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EP
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Prior art keywords
region
electrolyte membrane
nonwoven fibers
membrane
per unit
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German (de)
English (en)
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EP2642569A1 (fr
EP2642569A4 (fr
Inventor
Masahiro Mori
Shinya KIKUZUMI
Tsutomu Kawashima
Yasuhiro Ueyama
Kazunori Kubota
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Panasonic Corp
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Panasonic Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrolyte membrane for solid polymer fuel cell reinforced with nonwoven fibers, a membrane electrode assembly having the electrolyte membrane for solid polymer fuel cell, and a solid polymer fuel cell.
  • a fuel cell is structured as follows: joining a catalyst layer to an electrolyte membrane that causes a power generation reaction; clamping the joined catalyst layer and the electrolyte membrane between separators to obtain one module; and stacking the module by the required number of pieces.
  • the electrolyte membrane is fixed to an injection mold product functioning as a fixing seal (gasket) preventing leakage of the fuel gas, the injection mold product being mainly a resin-made frame-like frame element. Further, the electrolyte membrane fixed to the frame element is clamped between the separators, to form a module.
  • a proton conductive ion exchange membrane is used as the electrolyte membrane for solid polymer fuel cell.
  • a cation exchange membrane made of perfluorocarbon polymer having a sulfonate group (hereinafter referred to as the "sulfonate group-type perfluorocarbon polymer”) is widely taken into consideration for its excellent basic characteristic.
  • What is required as a practical electrolyte membrane for fuel cell is a membrane with low ohmic loss. The membrane ohmic loss depends on the electrical conductivity of the electrolyte polymer.
  • the electrolyte membrane with a high sulfonate group concentration itself greatly expands when impregnated with water, and tends to invite various disadvantages.
  • the size of the membrane increases by the water generated upon a power generation reaction or by the water vapor supplied with the fuel gas. Then, the increase in the size of the membrane becomes "wrinkles". The wrinkles bury the groove of the separators, to hinder the gas flow. Further, repetitive stop of the operation causes the membrane to repetitively expand and contract. This results in generation of crack in the membrane or the electrode joined to the membrane, to invite a reduction in the cell performance.
  • the conventional membrane electrode assembly employs a solid polymer electrolyte membrane including therein a porous sheet as the reinforce member.
  • Another proposal is an electrolyte membrane including therein nonwoven fibers of polyvinylidene fluoride copolymer as the reinforce member in place of the porous sheet (for example, see Patent Document 2).
  • the gas concentration is high. Accordingly, the power generation reaction actively occurs. That is, water is generated also by a great amount near the fuel gas inflow port, and the variation amount of the electrolyte membrane between expansion and dry contraction becomes great. This causes occurrence of a crack at the electrolyte membrane. Therefore, there is a problem that a reduction in the cell performance is invited.
  • a method for solving such problems for example, what can be considered is a method for increasing the thickness of a porous sheet disposed as the reinforce member in an electrolyte membrane, or a method for suppressing the variation in the size of the electrolyte membrane attributed to the expansion and contraction of the electrolyte membrane by increasing the strength of the porous sheet by reducing the holes formed in the porous sheet.
  • a method for increasing the thickness of a porous sheet disposed as the reinforce member in an electrolyte membrane or a method for suppressing the variation in the size of the electrolyte membrane attributed to the expansion and contraction of the electrolyte membrane by increasing the strength of the porous sheet by reducing the holes formed in the porous sheet.
  • such a method involves the technical contradiction. That is, such a method invites a reduction in proton conductivity of the electrolyte membrane, which influences the power generating characteristic of the fuel cell.
  • An object of the present invention is to provide an electrolyte membrane for solid polymer fuel cell with suppressed deterioration of the membrane attributed to variations of the size of the membrane which occurs when the electrolyte membrane is impregnated with water, without reducing the proton conductivity, and with stable fuel cell performance that endures for a long period.
  • an electrolyte membrane for solid polymer fuel cell includes:
  • a mass per unit area of the nonwoven fibers of the power generating region may increase as placing a distance from the center to outer region.
  • the nonwoven fibers may have a mass per unit area in a region having a width corresponding to 10% of a length of a side of the power generating region from the gasket frame which is greater than the mass per unit area in the region corresponding to the center portion of the power generating region.
  • nonwoven fibers may have a mass per unit area in a region corresponding to a fuel gas inlet of solid fuel cell to which the electrolyte membrane is adaptable, the mass per unit area being greater than the mass per unit area in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a mass per unit area in a region having a width corresponding to 30% of a length of the power generating region provided with the fuel gas inlet of solid fuel cell to which the electrolyte membrane is adaptable, the mass per unit area being greater than the mass per unit area in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a mass per unit area in a region corresponding to a fuel gas outlet of solid fuel cell to which the electrolyte membrane is adaptable, the mass per unit area being greater than the mass per unit area in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a mass per unit area in a region having a width corresponding to 30% of a length of a side of the power generating region provided with the fuel gas outlet of solid fuel cell to which an electrolyte membrane is adaptable, the mass per unit area being greater than the mass per unit area in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a mass per unit area in the region corresponding to the gasket frame region and the region corresponding to at least part of the peripheral portion of the gasket frame region which is smaller than 15 times as great as the mass per unit area in the region corresponding to the center portion of the power generating region.
  • the reinforce membrane may have a thickness in the region corresponding to the gasket frame region and the region corresponding to at least part of the peripheral portion of the region corresponding to the gasket frame region which is greater than and 15 times or less of a thickness in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a fiber diameter in the region corresponding to the gasket frame region and the region corresponding to at least part of the peripheral portion of the region corresponding to the gasket frame region which is greater than and 15 times or less of a fiber diameter in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a voidage in the region corresponding to at least part of the peripheral portion of the gasket frame which is lower than and 1/15 times or more of a voidage in the region corresponding to the center portion of the power generating region.
  • the nonwoven fibers may have a mass per unit area of 0.1 mg/cm 2 or more in the region corresponding to the center portion of the power generating region.
  • nonwoven fibers may contain polyvinylidene fluoride copolymer.
  • nonwoven fibers may be prepared through electrospinning.
  • the electrolyte may be a proton conductive ion exchange membrane.
  • An membrane electrode for solid polymer fuel cell assembly of the present invention includes the electrolyte membrane for solid polymer fuel cell and a module having the electrolyte membrane for solid polymer fuel cell fixed to a gasket and clamped between separators.
  • a solid polymer fuel cell of the present invention includes at least one cell, the cell being structured with the membrane electrode assembly for solid polymer fuel cell and a pair of anode separator and cathode separator clamping the membrane electrode for solid polymer fuel cell assembly.
  • the electrolyte membrane for solid polymer fuel cell of the present invention without inviting a reduction in proton conductivity, deterioration of the membrane attributed to the membrane variations of size when the electrolyte membrane is impregnated with water can be suppressed. Further, durability of the electrolyte membrane can be improved, and an excellent performance of the fuel cell can be secured for a long period.
  • Fig. 1 is a schematic diagram of a membrane integrated frame element 1 using an electrolyte membrane for solid polymer fuel cell (hereinafter referred to as the electrolyte membrane) 2 according to a first embodiment of the present invention.
  • Fig. 2 is a schematic diagram of cross section A-A' of the electrolyte membrane 2 according to the first embodiment shown in Fig. 1 .
  • the electrolyte membrane 2 is made of nonwoven fibers of polyvinylidene fluoride copolymer (hereinafter referred to as PVDF) and ion exchange resin packed in voids of the nonwoven fibers.
  • the nonwoven fibers function as a reinforce member.
  • the nonwoven fibers may be referred to also as a reinforce membrane 22 structuring the electrolyte membrane 2.
  • the ion exchange resin is referred to also as a proton conductivity ion exchange membrane.
  • the electrolyte membrane 2 according to the first embodiment is particularly characterized in that the nonwoven fibers have non-uniform mass distribution in the plane of the electrolyte membrane.
  • the electrolyte membrane 2 is characterized in that the electrolyte membrane 2 includes therein a reinforce membrane 22 having a mass of the nonwoven fibers per unit area which is greater than the mass of the nonwoven fibers per unit area in a region 221 corresponding to the center portion of the gasket frame in a fuel gas inlet periphery region 211 and a region of a gasket frame peripheral portion 212 along sides 32 to 34 of the gasket frame with no fuel gas inlet 3.
  • the mass of the nonwoven fibers per unit area in the electrolyte membrane 2 in the region 211 near the fuel gas inlet and the peripheral portion 212 thereof is greater than the mass of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame, it is suitable for the case where the fuel cell is operated using fuel gas being humidified to have a humidity of 100%.
  • Fig. 17 is a schematic diagram showing a membrane integrated frame element 1 using an electrolyte membrane 2 having a reinforce membrane in which the mass of nonwoven fibers per unit area is uniform, as a reference example.
  • Fig. 18 is a schematic diagram showing the cross section of the membrane integrated frame element 1 using the electrolyte membrane 2 including a reinforce membrane 22 in which the mass of nonwoven fibers per unit area is uniform, as a reference example.
  • the membrane integrated frame element 1 is operated using the fuel gas humidified to have a humidity of 100%, when the fuel gas reaches the power generating region 21, the electrolyte membrane 2 is moisturized by water vapor delivered together with the gas near the fuel gas inlet 3, and hence a power generation reaction occurs actively.
  • the water vapor delivered together with the fuel gas moisturizes the electrolyte membrane 2 and the water generated by power generation moisturizes the electrolyte membrane 2.
  • deterioration of the electrolyte membrane is accelerated particularly near the fuel gas inlet 3 in the power generating region 21, because the expansion of the electrolyte membrane 2 performs and variations of size attributed to contraction is caused by dryness in the situation where the fuel cell stops operation.
  • the electrolyte membrane 2 is retained by gaskets 5, and the electrolyte membrane 2 and the gaskets 5 are clamped by separators (not shown). Power is generated at a power generating region 21 not being fixed to the gaskets 5 of the electrolyte membrane 2. Water is generated by the power generation, and the power generating region 21 in the electrolyte membrane 2 repeats expansion due to water impregnation and contraction due to dryness when operation is stopped. Therefore, deterioration of the membrane is invited at a fixed boundary portion 51 between the sides 32 to 34 of the gasket frame and the electrolyte membrane 2.
  • the electrolyte membrane 2 has the reinforce membrane 22 including PVDF nonwoven fibers, which function as a whole as the reinforce member, with non-uniform mass distribution. Further, with the electrolyte membrane 2, at the gas inlet periphery 211 and the gasket frame peripheral portion 212 where expansion and contraction frequently take place, particularly the mass of PVDF nonwoven fibers per unit area is greater than the mass of nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame. Since the PVDF nonwoven fibers function as the reinforce member of the electrolyte membrane 2, expansion incurred by impregnation of water can be restricted. Thus, deterioration of the membrane can be suppressed.
  • the deterioration of the electrolyte membrane 2 is significant at the region 211 near the fuel gas inlet. Accordingly, with the electrolyte membrane 2 according to the first embodiment, it is desirable that the mass of the nonwoven fibers per unit area of the reinforce membrane 22 of the region having a length of 10% to 40% of the distance from the fuel gas inlet 3 to the side 34 of the gasket frame opposing to the side 31 of the gasket frame provided with the fuel gas inlet 3 is set to be greater than the mass of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame. Thus, the electrolyte membrane 2 deteriorating significantly at the fuel gas inlet periphery can be reinforced.
  • the PVDF nonwoven fibers according to the first embodiment can be prepared through electrospinning.
  • the mass of the PVDF nonwoven fibers per unit area prepared through electrospinning is the smallest at the center portion 221 of the power generating region 21 and the greatest at the fuel gas inlet periphery 211 and the periphery of the sides 32 to 34 of the gasket frame.
  • the PVDF nonwoven fibers are in the shape in which the fibers are overlapping one another in a web-like manner, the mass of the nonwoven fibers per unit area being desirably 0.1 mg/cm 2 or more. When the mass of the nonwoven fibers per unit area is small, variations of size of the electrolyte membrane 2 due to expansion cannot be suppressed.
  • the mass per unit area is desirably 1.5 mg/cm 2 or less.
  • the mass per unit area is based on an assumption that the thickness of the electrolyte membrane when prepared as the electrolyte membrane is 5 ⁇ m to 40 ⁇ m.
  • the mass difference of the reinforce membrane per unit area is 15 times, i.e., the greatest.
  • variations of the size due to dryness and moisture can be suppressed by reducing deterioration of the membrane attributed to variations of the size of membrane when the electrolyte membrane is impregnated with water.
  • the mass difference of the nonwoven fibers per unit area in the reinforce membrane 22 is greater than 15 times described above, the smallest mass per unit area turns out to be 0.1 mg/cm 2 or less, whereby variations of the size due to dryness and moisture cannot be suppressed.
  • the greatest mass per unit area turns out to be 1.5 mg/cm 2 or more, whereby proton conductivity is reduced.
  • the thickness of the nonwoven fibers should be increased. In the case where the thickness of the electrolyte membrane is further greater also, the mass difference of the nonwoven fibers per unit area in the reinforce membrane should be set to 15 times or less.
  • the electrolyte membrane 2 including therein the PVDF nonwoven fibers can generate power as a fuel cell, by protons propagating through the electrolyte material portion packed in the void portion with no PVDF nonwoven fibers.
  • the mass of the PVDF nonwoven fibers per unit area is small and the proportion of the void portion with no PVDF nonwoven fibers is great. Therefore, proton propagation actively occurs and sufficient power generation is performed.
  • the mass of the PVDF nonwoven fibers per unit area is great. Therefore, the PVDF nonwoven fibers serving as the reinforce member of the electrolyte membrane 2 are great in number, whereby variations of size due to expansion and contraction can be suppressed and durability of the electrolyte membrane 2 can be secured.
  • the electrolyte membrane 2 reaches approximately 80C° when the fuel cell is in operation, it is preferable to employ PVDF as the nonwoven fibers, for its full heat resistance even in the temperature range noted above, chemically stable property, and capability of being turned into nonwoven fibers through electrospinning.
  • nonwoven fibers in addition to PVDF, copolymer made of a plurality of units of monomer structuring polymer such as PVDF or PVF, e.g., polyvinyl fluoride polymer (hereinafter referred to as PVF), mixture of such polymers and the like can be used.
  • PVF polyvinyl fluoride polymer
  • the nonwoven fibers should be made of a material being heat resistant and chemically resistant, and being capable of being subjected to electrospinning.
  • the nonwoven fibers are further preferably made of a hydrophobic material. Disposing the nonwoven fibers made of a hydrophobic material in the electrolyte membrane 2, the unnecessary water generated in the electrolyte membrane 2 by a power generation reaction can be discharged.
  • the mechanical properties such as tensile strength and elongation are excellent.
  • the molecular weight of PVDF used as the nonwoven fibers desirably falls within the range of 150000 to 550000. When the molecular weight is excessively small, the mechanical strength reduces; when the molecular weight is excessively great, solubility reduces, and it becomes difficult to obtain a solution.
  • PVDF in order to subject PVDF to electrospinning to obtain nonwoven fibers, PVDF is dissolved using dimethylacetamide (hereinafter referred to as DMAc) as the solvent, to be turned into a solution.
  • the solvent may be dimethyl sulfoxide, dimethylformamide, acetone or the like.
  • DMAc dimethylacetamide
  • the desirable solution concentration range is 10% to 25%.
  • the solution concentration is low, sufficient fiber diameter cannot be obtained, and variations of size due to expansion and contraction of the electrolyte membrane 2 cannot be suppressed.
  • the solution concentration is higher than the range noted above, sufficient electrostatic burst cannot be achieved in obtaining the nonwoven fibers through electrospinning. The spaces among the fibers are eliminated, and hence proton conduction as one function of the electrolyte membrane 2 is inhibited.
  • Fig. 3 is a schematic diagram of the facility for obtaining the PVDF nonwoven fibers according to the first embodiment.
  • a PVDF solution 81 is put into a syringe 82.
  • a solution discharge nozzle 83 is provided at the bottom portion of the syringe 82.
  • a needle-like nozzle 83 is used as the solution discharge nozzle.
  • the desirable nozzle inner diameter falls within a range of ⁇ 0.18 mm to ⁇ 0.42 mm. When the nozzle inner diameter is small, the discharge amount becomes small. Therefore, the productivity reduces. Further, when the nozzle inner diameter is increased, the discharge amount becomes great and the electrostatic burst cannot take place appropriately. Hence, fibers cannot be obtained.
  • an air pulse dispenser (not shown) may be used for discharging.
  • a desirable range of the solution delivery pressure is from 10 kPa to 50 kPa.
  • the solution delivery pressure is low, the PVDF solution 81 is not discharged enough and the productivity reduces. Further, when the solution delivery pressure is increased, the discharge amount becomes great and the electrostatic burst cannot take place appropriately. Hence, fibers cannot be obtained. Since the discharge amount varies depending on the viscosity of the solution, when the viscosity is high, the solution delivery pressure should be increased; when the viscosity is low, the solution delivery pressure should be reduced. Thus, the solution delivery pressure should be controlled such that an appropriate discharge amount is achieved.
  • the electric field between the nozzle 83 and the collector 84 desirably falls within a range of 10 kV to 50 kV.
  • the electric field is weak, sufficient electrostatic burst cannot be achieved, and hence appropriate fibers cannot be obtained.
  • the electric field is intense, the time taken by the PVDF solution 81 discharged from the nozzle 83 to reach the collector 84 becomes short. Accordingly, sufficient electrostatic burst cannot be achieved and hence appropriate fibers cannot be obtained.
  • the distance 831 between the tip of the nozzle 83 and the collector 84 desirably falls within a range of 90 mm to 160 mm.
  • the distance 831 between the tip of the nozzle 83 and the collector 84 is short, the time taken by the PVDF solution 81 discharged from the nozzle 83 to reach the collector 84 becomes short. Accordingly, sufficient electrostatic burst cannot be achieved, and appropriate fibers cannot be obtained.
  • the electrostatic burst is influenced by the viscosity or amount of the solution.
  • the optimum applied voltage or the distance between the nozzle 83 and the collector 84 can be determined based on the degree of dryness of the solvent of the solution.
  • the electrostatic burst is insufficient. Accordingly, the discharge amount from the nozzle 83 should be reduced to achieve an appropriate discharge amount. Further, an increase in the distance between the nozzle 83 and the collector 84 likewise facilitates an occurrence of appropriate electrostatic burst.
  • the distance between the nozzle 83 and the collector 84 may be increased.
  • a plurality of nozzles may be used for improving productivity.
  • the distance between the nozzles is desirably 10 mm or more.
  • the adjacent nozzles and the charged PVDF solution 81 are influenced by the charges of each other's. Then, sufficient electrostatic burst cannot be achieved and hence appropriate fibers cannot be obtained.
  • Fig. 4 is a schematic diagram of a nozzle scan track according to the first embodiment.
  • the nozzle 83 is scanned at a constant speed on the collector 84 along a nozzle scanning pattern 832 so that a layer of nonwoven fibers of uniform thickness is obtained.
  • the scanning speed is desirably 50 mm/s or less.
  • the nonwoven fibers accumulated on the collector 84 are deposited under the tensile force attributed to scanning. Therefore, the internal stress is remained, and this may cause the electrolyte membrane 2 to contract.
  • the present invention is not limited thereto, and a block-like nozzle 83 provided with a plurality of discharging holes may be used. This makes it possible to form uniform electrostatic field without being influenced by the difference among individual nozzles 83, and to form homogeneous nonwoven fibers.
  • Fig. 5A shows the coating weight distribution (mass distribution) of the nonwoven fibers per unit area in the plane of the electrolyte membrane according to the first embodiment
  • Fig. 5B is a schematic diagram of the thickness distribution of the nonwoven fibers
  • Figs. 6A to 6C are schematic diagrams of a PVDF nonwoven fibers preparation process according to the first embodiment
  • Fig. 7 is a schematic diagram of the nozzle scan track in providing thickness variations to the nonwoven fibers shown in Fig. 6C
  • Fig. 8 is a schematic diagram of the density distribution of the nonwoven fibers in the thickness direction of the electrolyte membrane 2 according to the first embodiment.
  • the distribution of the nonwoven fibers 86 becomes asymmetric distribution 61 about the center of the thickness of the electrolyte membrane 2.
  • non-uniform mass distribution of the nonwoven fibers in the plane of the electrolyte membrane 2 may be implemented as shown in other example shown in Fig. 9A to 9D . In the following, the other example is described.
  • the electrolyte membrane 2 whose mass distribution 62 of the nonwoven fibers per unit area is line symmetric in the thickness direction of the membrane relative to the thickness center portion of the electrolyte membrane 2 can be obtained.
  • the difference in variations of size of the electrolyte membrane 2 due to expansion and contraction at the front surface and the back surface can be reduced.
  • Fig. 11 is a schematic diagram of an applying process of electrolyte solution 87 according to the first embodiment.
  • Figs. 11A to 11F the electrolyte solution may be applied as in other example shown in Fig. 12A to 12E .
  • a description will be given of the other example.
  • the process proceeds similarly to Fig. 11A to Fig. 11F , and then the process following the Fig. 11F , i.e., peeling, is shown.
  • Figs. 12A and 12B are substantially identical to Fig. 11A and11B.
  • electrolyte solution may be applied as shown in other example shown in Figs. 13A to 13C .
  • a description will be given of the other example.
  • the PVDF nonwoven fibers 86 may be formed in the state where the electrolyte solution 87 is dried. Alternatively, the PVDF nonwoven fibers 86 may be formed on the electrolyte solution 87 not being dried. In the latter case, when the PVDF nonwoven fibers 86 are formed on the electrolyte solution 87 not being dried, the formed PVDF nonwoven fibers 86 sink into the electrolyte solution 87 having been applied in advance.
  • the PVDF nonwoven fibers 86 exist across the electrolyte solution 87 having been applied in advance to the PET substrate 85 and the electrolyte solution 87 applied after the PVDF nonwoven fibers 86 are formed.
  • the interface between the electrolyte solution 87 having been applied in advance and the electrolyte solution 87 applied after the PVDF nonwoven fibers 86 are formed is reinforced by the PVDF nonwoven fibers 86.
  • the mass of the nonwoven fibers per unit area is controlled.
  • the present invention is also applicable to the electrolyte membrane with small thickness.
  • a reduction in the fiber diameter of each of the nonwoven fibers can be realized by the process conditions such as: reducing the solution concentration; reducing the nozzle diameter; reducing the solution delivery pressure; increasing the applied voltage; increasing the spinning distance, and the like.
  • the first embodiment is applied to the membrane electrode assembly having the serpentine-like fuel gas flow channel in the separator, it is also applicable to a membrane electrode assembly having a straight fuel gas flow channel.
  • Fig. 14 is a schematic diagram of a membrane integrated frame element 1 using an electrolyte membrane 2 for solid polymer fuel cell according to a second embodiment of the present invention.
  • Fig. 15 is a schematic diagram of cross section C-C' of the electrolyte membrane 2 according to the second embodiment shown in Fig. 14 .
  • the electrolyte membrane 2 according to the second embodiment is identical in that the nonwoven fibers have non-uniform mass distribution in the plane of the electrolyte membrane.
  • the electrolyte membrane 2 according to the second embodiment is particularly characterized by including therein a reinforce membrane 22 in which the mass of nonwoven fibers per unit area is greater than the mass of the nonwoven fibers per unit area in a region 221 corresponding to the center portion of the gasket frame in a region 231 near the fuel gas outlet and a gasket frame peripheral portion 212.
  • the electrolyte membrane 2 according to the second embodiment is suitable for the case in which the fuel cell is operated using the fuel gas in the low-humidified state, since the mass of the nonwoven fibers per unit area in the region 231 near the fuel gas outlet and the gasket frame peripheral portion 212 is greater than the mass of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame.
  • Fig. 17 is a schematic diagram of a membrane electrode assembly according to a reference example.
  • Fig. 18 is a schematic diagram showing the cross section of a membrane integrated frame element 1 using an electrolyte membrane 2 according to the reference example.
  • the membrane integrated frame element 1 according to the reference example is operated using the fuel gas in the low-humidified state, the water generated by a power generation reaction near the fuel gas inlet 3 shifts toward the fuel gas outlet 4, to moisturize the electrolyte membrane 2 around the fuel gas outlet 4. Accordingly, a power generation reaction actively occurs in the electrolyte membrane 2 around the fuel gas outlet 4. Further, the moisturization of the electrolyte membrane 2 by the water generated by the power generation reaction around the fuel gas outlet 4 also occurs.
  • the water content in the electrolyte membrane 2 at the fuel gas outlet 4 becomes relatively greater than the water content in the electrolyte membrane 2 at the fuel gas inlet 3 in the power generating region 21 of the electrolyte membrane 2 in a single membrane integrated frame element 1.
  • the electrolyte membrane 2 is retained by gaskets 5, and the electrolyte membrane 2 and the gaskets 5 are clamped by the separators (not shown). Power is generated at the power generating region 21 not being fixed to the gaskets 5 of the electrolyte membrane 2. Water is generated by the power generation, and the power generating region 21 in the electrolyte membrane 2 repeats expansion due to water impregnation and contraction due to dryness when operation is stopped. Therefore, deterioration of the membrane is invited at a fixed boundary portion 51 between the sides 31 to 33 of the gasket frame and the electrolyte membrane 2.
  • the electrolyte membrane 2 has the reinforce membrane 22 containing the PVDF nonwoven fibers, which function as a whole as the reinforce member, with non-uniform mass distribution. Further, with the electrolyte membrane 2, at the fuel gas outlet periphery 231 and the gasket frame peripheral portion 212 where expansion and contraction frequently take place, particularly the mass of the PVDF nonwoven fibers per unit area is great. Accordingly, in particular, expansion caused by impregnation of water at the electrolyte membrane at the fuel gas outlet periphery can be restricted, whereby deterioration of the membrane can be suppressed.
  • the deterioration of the electrolyte membrane 2 is significant at the fuel gas outlet periphery 231. Accordingly, with the electrolyte membrane 2 according to the second embodiment, it is desirable that the mass of the nonwoven fibers of the reinforce membrane 22 per unit area of the region having a length of 10% to 40% of the distance from the fuel gas outlet 4 to the side 31 of the gasket frame opposing to the side 34 of the gasket frame provided with the fuel gas outlet 4 is set to be greater than the mass of the nonwoven fibers per unit area of the region 221 corresponding to the center portion of the gasket frame. Thus, the electrolyte membrane 2 deteriorating significantly at the fuel gas outlet periphery 231 can be reinforced.
  • the PVDF nonwoven fibers according to the second embodiment can be prepared through electrospinning.
  • the mass of the PVDF nonwoven fibers per unit area prepared through electrospinning is the smallest at the center portion 221 of the power generating region 21 and the greatest at the fuel gas outlet periphery 231 and the periphery of the sides 31 to 33 of the gasket frame.
  • the PVDF nonwoven fibers are in the shape in which the fibers are overlapping one another in a web-like manner, the mass of the nonwoven fibers per unit area being desirably 0.1 mg/cm 2 or more. When the mass of the nonwoven fibers per unit area is small, variations of size of the electrolyte membrane 2 due to expansion cannot be suppressed.
  • the electrolyte membrane 2 including therein the PVDF nonwoven fibers can generate power as a fuel cell, by protons propagating through the electrolyte material portion packed in the void portion with no PVDF nonwoven fibers.
  • the mass of the PVDF nonwoven fibers per unit area is small and the proportion of the void portion with no PVDF nonwoven fibers is great. Therefore, proton propagation actively occurs and sufficient power generation is performed.
  • the mass of the PVDF nonwoven fibers per unit area is greater than the mass of the reinforce member of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame.
  • the PVDF nonwoven fibers functioning as the electrolyte membrane 22 become great in number, whereby variations of size due to expansion and contraction can be suppressed and durability of the electrolyte membrane can be secured.
  • the electrolyte membrane 2 reaches approximately 80C° when the fuel cell is in operation, it is preferable to employ PVDF as the nonwoven fibers, for its full heat resistance even in the temperature range noted above, chemically stable property, and capability of being turned into nonwoven fibers through electrospinning.
  • nonwoven fibers in addition to PVDF, copolymer made of a plurality of units of monomer structuring polymer such as PVDF or PVF, e.g., polyvinyl fluoride polymer (hereinafter referred to as PVF), mixture of such polymers and the like can be used.
  • PVF polyvinyl fluoride polymer
  • the nonwoven fibers should be made of a material being heat resistant and chemically resistant, and being capable of being subjected to electrospinning.
  • the nonwoven fibers are further preferably made of a hydrophobic material. Disposing the nonwoven fibers made of a hydrophobic material in the electrolyte membrane 2, the unnecessary water generated in the electrolyte membrane 2 by a power generation reaction can be discharged.
  • the mechanical properties such as tensile strength and elongation are excellent.
  • the molecular weight of PVDF used as the nonwoven fibers desirably falls within the range of 150000 to 550000. When the molecular weight is excessively small, the mechanical strength reduces; when the molecular weight is excessively great, solubility reduces, and it becomes difficult to obtain a solution.
  • PVDF in order to subject PVDF to electrospinning to obtain nonwoven fibers, PVDF is dissolved using dimethylacetamide (hereinafter referred to as DMAc) as the solvent, to be turned into a solution.
  • the solvent may be dimethyl sulfoxide, dimethylformamide, acetone or the like.
  • DMAc dimethylacetamide
  • the desirable solution concentration range is 10% to 25%.
  • the solution concentration is low, sufficient fiber diameter cannot be obtained, and variations of size due to expansion and contraction of the electrolyte membrane 2 cannot be suppressed.
  • the solution concentration is higher than the range noted above, sufficient electrostatic burst cannot be achieved in obtaining the nonwoven fibers through electrospinning. The spaces among the fibers are eliminated, and hence proton conduction as one function of the electrolyte membrane 2 is inhibited.
  • a PVDF solution 81 is put into a syringe 82.
  • a solution discharge nozzle 83 is provided at the bottom portion of the syringe 82.
  • a needle-like nozzle 83 is used as the solution discharge nozzle.
  • the desirable nozzle inner diameter falls within a range of ⁇ 0.18 mm to ⁇ 0.42 mm. When the nozzle inner diameter is small, the discharge amount becomes small. Therefore, productivity reduces. Further, when the nozzle inner diameter is increased, the discharge amount becomes great and the electrostatic burst cannot take place appropriately. Hence, fibers cannot be obtained.
  • an air pulse dispenser (not shown) may be used for discharging.
  • a desirable range of the solution delivery pressure in the syringe 82 for delivering the PVDF solution 81 is from 10 kPa to 50 kPa.
  • the solution delivery pressure is low, the PVDF solution 81 is not discharged enough and the productivity reduces.
  • the solution delivery pressure is increased, the discharge amount becomes great and the electrostatic burst cannot take place appropriately. Hence, fibers cannot be obtained. Since the discharge amount varies depending on the viscosity of the solution, when the viscosity is high, the solution delivery pressure should be increased; when the viscosity is low, the solution delivery pressure should be reduced. Thus, the solution delivery pressure should be controlled such that an appropriate discharge amount is achieved.
  • voltage is applied to the nozzle 83, and a collector 84 collecting the fibers is connected to the ground.
  • the electric field between the nozzle 83 and the collector 84 desirably falls within a range of 10 kV to 50 kV.
  • the electric field is weak, sufficient electrostatic burst cannot be achieved, and hence appropriate fibers cannot be obtained.
  • the electric field is intense, the time taken by the PVDF solution 81 discharged from the nozzle 83 to reach the collector 84 becomes short. Accordingly, sufficient electrostatic burst cannot be achieved and hence appropriate fibers cannot be obtained.
  • positive voltage is applied to the nozzle 83 in the second embodiment, negative charge should be applied depending on the material from which nonwoven fibers are to be obtained. Accordingly, the polarity of voltage to be applied should be selected depending on the material.
  • the distance 831 between the tip of the nozzle 83 and the collector 84 desirably falls within a range of 90 mm to 160 mm.
  • the distance 831 between the tip of the nozzle 83 and the collector 84 is short, the time taken by the PVDF solution 81 discharged from the nozzle 83 to reach the collector 84 becomes short. Accordingly, sufficient electrostatic burst cannot be achieved, and appropriate fibers cannot be obtained.
  • the electrostatic burst is influenced by the viscosity or amount of the solution.
  • the optimum applied voltage or the distance between the nozzle 83 and the collector 84 can be adjusted depending on the degree of dryness of the solvent of the solution.
  • the electrostatic burst is insufficient. Accordingly, the discharge amount from the nozzle 83 should be reduced to achieve an appropriate discharge amount. Further, an increase in the distance between the nozzle 83 and the collector 84 likewise facilitates an occurrence of appropriate electrostatic burst.
  • the distance between the nozzle 83 and the collector 84 may be increased.
  • the number of pieces of nozzle may be increased for improving productivity.
  • the distance between the nozzles is desirably 10 mm or more.
  • the adjacent nozzles or the charged PVDF solution 81 are influenced by the charges of each other's. Then, sufficient electrostatic burst cannot be achieved and hence appropriate fibers cannot be obtained.
  • the nozzle 83 is scanned at a constant speed on the collector 84 along a nozzle scanning pattern 833 so that a layer of nonwoven fibers of uniform thickness is obtained.
  • the scanning speed is desirably 50 mm/s or less.
  • the nonwoven fibers accumulated on the collector 84 are deposited under the tensile force attributed to the scanning speed. Therefore, stress is remained, and this may cause the electrolyte membrane 2 to contract.
  • a plurality of needle-like nozzles 83 are used in the second embodiment, a block-like nozzle 83 provided with a plurality of discharging holes may be used. This makes it possible to form homogeneous fibers without being influenced by the difference between individual nozzles 83.
  • Fig. 16 is a schematic diagram of the nozzle scan track in providing thickness variation to the nonwoven fibers according to the second embodiment.
  • the distribution of the nonwoven fibers 86 becomes asymmetric distribution 61 about the center of the thickness of the electrolyte membrane 2.
  • non-uniform mass distribution of the nonwoven fibers in the plane of the electrolyte membrane 2 may be implemented as shown in other example shown in Figs. 9A to 9D . In the following, the other example is described.
  • the electrolyte membrane 2 whose mass distribution 62 of the nonwoven fibers per unit area is line symmetric in the thickness direction of the membrane relative to the thickness center portion of the electrolyte membrane 2 can be obtained.
  • the difference in variations of size of the electrolyte membrane 2 due to expansion and contraction at the front surface and the back surface can be reduced.
  • the applying process of the electrolyte solution 87 shown in Fig. 11 may be performed also in the second embodiment.
  • Figs. 12A and 12B are substantially identical to Figs. 11A and 11B .
  • electrolyte solution may be applied as shown in other example shown in Figs. 13A to 13C .
  • a description will be given of the other example.
  • the PVDF nonwoven fibers 86 may be formed thereon.
  • the PVDF nonwoven fibers 86 may be formed on the electrolyte solution 87 not being dried. In the latter case, when the PVDF nonwoven fibers 86 are formed on the electrolyte solution 87 not being dried, the formed PVDF nonwoven fibers 86 sink into the electrolyte solution 87 having been applied in advance. Therefore, the PVDF nonwoven fibers 86 exist across the electrolyte solution 87 having been applied in advance to the PET substrate 85 and the electrolyte solution 87 applied after the PVDF nonwoven fibers 86 are formed.
  • the interface between the electrolyte solution 87 applied in advance and the electrolyte solution 87 applied after the PVDF nonwoven fibers 86 are formed is reinforced by the PVDF nonwoven fibers 86.
  • the mass of the nonwoven fibers per unit area is controlled.
  • the present invention is also applicable to the electrolyte membrane with small thickness.
  • a reduction in the fiber diameter of each of the nonwoven fibers can be realized by the process conditions such as: reducing the solution concentration; reducing the nozzle diameter; reducing the solution delivery pressure; increasing the applied voltage; increasing the spinning distance, and the like.
  • the second embodiment is applied to the membrane electrode assembly having the serpentine-like fuel gas flow channel in the separator, it is also applicable to a membrane electrode assembly having a straight fuel gas flow channel.
  • the pellet-form PVDF (available from Arkema, molecular weight 275000) was dissolved in DMAc. As the specific condition, 80g of DMAc was mixed with 20g of PVDF and agitated by a planetary mixer, to dissolve PVDF in DMAc.
  • a nonwoven fiber manufacturing apparatus (available from Panasonic Factory Solutions Co., Ltd.) used for electrospinning was prepared. Further, in connection with the nonwoven fiber manufacturing apparatus, a stainless steel-made nozzle of 24G (inner diameter 0.31 mm, outer diameter 0.57 mm, needle length 15 mm) was attached to the tip of a disposable syringe having a capacity of 10 mL. Under the condition in which: the distance from the collector to the nozzle was 120 mm; the applied voltage between the collector and the nozzle was 20 kV; and the solution delivery pressure was 30 kPa, nonwoven fibers were prepared. The diameter of each of the nonwoven fibers generated on the collector had a distribution of 400 nm to 1100 nm, and the average fiber diameter was 700 nm. Further, the voidage of nonwoven fibers was approximately 90%.
  • Nafion solution SE-20092, available from DuPont was used as the electrolyte solution.
  • the nonwoven fibers were impregnated with the electrolyte solution.
  • Impregnation was carried out with the electrolyte solution of an appropriate volume, such that a membrane having a thickness of 30 ⁇ m was obtained, through drying and calcining following the impregnation. The drying and calcining were carried out for one hour at 120°C.
  • the electrolyte membrane 2 prepared through the present invention had the power generating region 21 of 160 mm square, and the thickness of the electrolyte membrane 2 was 30 ⁇ m.
  • the region 211 near the fuel gas inlet extends by 48 mm from the side 31 of the gasket frame provided with the fuel gas inlet 3, and the peripheral region 212 of the gasket frame extends by 16 mm from the sides 32 to 34 of the gasket frame not provided with the fuel gas inlet 3.
  • the resultant mass of the reinforce membrane 22 per unit area disposed in the electrolyte membrane 2 was 1.28 mg/cm 2 , and the resultant thickness of the reinforce membrane was 25 ⁇ m in the region 211 near the fuel gas inlet and the peripheral region 212 of the gasket frame.
  • the resultant mass of the reinforce membrane 22 per unit area arranged in the electrolyte membrane 2 was 0.26 mg/cm 2 and the resultant thickness of the reinforce membrane was 3 ⁇ m.
  • a nonwoven fiber manufacturing apparatus (available from Panasonic Factory Solutions Co., Ltd.) used for electrospinning was prepared.
  • a stainless steel-made nozzle of 24G (inner diameter 0.31 mm, outer diameter 0.57 mm, needle length 15 mm) was attached to the tip of a disposable syringe having a capacity of 10mL.
  • the distance from the collector to the nozzle was 120 mm; the applied voltage between the collector and the nozzle was 20 kV; and the solution delivery pressure was 30 kPa, nonwoven fibers were prepared.
  • the diameter of each of the nonwoven fibers generated on the collector had a distribution of 400 nm to 1100 nm, and the average fiber diameter was 700 nm. Further, the voidage of the nonwoven fibers was approximately 90%.
  • Fig. 19 is a schematic diagram of a membrane integrated frame element 1 using an electrolyte membrane 2 for solid polymer fuel cell according to a third embodiment of the present invention.
  • the electrolyte membrane 2 according to the third embodiment is identical in that the nonwoven fibers have non-uniform mass distribution in the plane of the electrolyte membrane 2.
  • the electrolyte membrane 2 according to the third embodiment is particularly characterized in that the mass of the nonwoven fibers per unit area in a region 212 being a partial region of the peripheral portion of a side 31 of the gasket frame near the fuel gas inlet is greater than the mass of the nonwoven fibers per unit area in a region 221 corresponding to the center portion of the gasket frame.
  • the region 212 corresponds to the width of 10% of the length from the side 31 of the gasket frame to the opposing side 34 of the gasket frame.
  • the electrolyte membrane 2 has a reinforce membrane 22 including PVDF nonwoven fibers, which function as a whole as the reinforce member, with non-uniform mass distribution. Further, with the electrolyte membrane 2, at the partial region 212 of the peripheral portion of the side 31 of the gasket frame of the gas inlet periphery where expansion and contraction frequently take place, particularly the mass of PVDF nonwoven fibers per unit area is greater than the mass of nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame. Since the PVDF nonwoven fibers function as the reinforce member of the electrolyte membrane 2, expansion incurred by impregnation of water can be restricted. Thus, deterioration of the membrane can be suppressed.
  • Fig. 20 is a schematic diagram of a membrane integrated frame element 1 using an electrolyte membrane 2 for solid polymer fuel cell according to a fourth embodiment of the present invention.
  • the electrolyte membrane 2 according to the fourth embodiment is identical in that the nonwoven fibers have non-uniform mass distribution in the plane of the electrolyte membrane 2. Further, the electrolyte membrane 2 according to the fourth embodiment is characterized in that the mass of the nonwoven fibers per unit area in an outer circumferential portion 212 of a side 31 of the gasket frame is greater than the mass of the nonwoven fibers per unit area of a region 221 corresponding to the center portion of the gasket frame.
  • outer circumferential portion 212 corresponds to the width corresponding to 10% of the length from a side 31 of the gasket frame to the opposing side 34 of the gasket frame, and to 10% of the width of the length from a side 32 of the gasket frame to the opposing side 33 of the gasket frame.
  • the electrolyte membrane 2 has a reinforce membrane 22 containing the PVDF nonwoven fibers functioning, as a whole, as a reinforce member of non-uniform mass distribution. Further, with the electrolyte membrane 2, at the outer circumferential portion 212 of the side 31 of the gasket frame where expansion and contraction frequently take place, particularly the mass of the PVDF nonwoven fibers per unit area is greater than the mass of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame. Since the PVDF nonwoven fibers function as the reinforce member of the electrolyte membrane 2, expansion caused by impregnation of water can be restricted. Thus, deterioration of the membrane can be suppressed.
  • Fig. 21 is a schematic diagram of a membrane integrated frame element 1 using an electrolyte membrane 2 for solid polymer fuel cell according to a fifth embodiment of the present invention.
  • the electrolyte membrane 2 according to the fifth embodiment is identical in that the nonwoven fibers have non-uniform mass distribution in the plane of the electrolyte membrane 2. Further, the electrolyte membrane 2 according to the fifth embodiment is characterized in that the mass of the nonwoven fibers per unit area in a gas inlet periphery 211 near the fuel gas inlet is greater than the mass of the nonwoven fibers per unit area in a region 221 corresponding to the center portion of the gasket frame. Note that the region of the fuel gas inlet periphery 211 corresponds to the width corresponding to 30% of the length from a side 31 of the gasket frame to the opposing side 34 of the gasket frame.
  • the electrolyte membrane 2 has a reinforce membrane 22 containing the PVDF nonwoven fibers functioning, as a whole, as a reinforce member of non-uniform mass distribution. Further, with the electrolyte membrane 2, at the gas inlet periphery 211 near the fuel gas inlet where expansion and contraction frequently take place, particularly the mass of the PVDF nonwoven fibers per unit area is greater than the mass of the nonwoven fibers per unit area in the region 221 corresponding to the center portion of the gasket frame. Since the PVDF nonwoven fibers function as the reinforce member of the electrolyte membrane 2, expansion caused by impregnation of water can be restricted. Thus, deterioration of the membrane can be suppressed.
  • Fig. 22 is a perspective view schematically showing, in a partially exploded manner, the structure of a solid polymer fuel cell 100 according to a sixth embodiment using the electrolyte membrane 2 for solid polymer fuel cell according to the first to fifth embodiments of the present invention.
  • the solid polymer fuel cell 100 is structured with a plurality of cells (electric cell modules) 10 being stacked.
  • a current collector to each of the outermost layers on the opposite sides of the cell 10, a current collector, an insulating plate, and an end plate (termination plate) are attached.
  • the cell 10 is fastened by fastening bolts and nuts (both not shown) that are inserted into bolt holes 14 from the opposite ends.
  • 60 pieces of the cells 10 are stacked, and the bolts and the nuts inserted into the bolt holes 14 are fastened under a fastening force of 10 kN.
  • the present invention is applicable to the case where the solid polymer fuel cell is structured with a single cell.
  • the cell 10 is made of an anode separator 12 and a cathode separator 13 being a pair of electrical conductivity separators, between which a membrane-frame assembly 1 is interposed. More specifically, the cell 10 is structured as follows: the opposite surfaces of a frame element 6 disposed at the peripheral portion of the membrane-frame assembly 1 are clamped by the pair of separators 12 and 13 via gaskets 5, which are exemplary sealing members disposed at the opposite surfaces of the frame element 6. Thus, diffusion layers 15 provided at the outermost sides of the electrode layer of the membrane electrode assembly 20 abut on the front surfaces of the separators 12 and 13.
  • a fuel gas flow channel and an oxidizing gas flow channel are defined by a diffusion layer abutting portion 24A of a fuel gas flow channel groove 21 of the anode separator 12, a diffusion layer abutting portion 34A of the oxidizing gas flow channel groove 34 of the cathode separator 13, and a diffusion layer 15.
  • the fuel gas flowing through the diffusion layer abutting portion 24A is brought into contact with the diffusion layer 15 on the anode separator 12 side, to cause an electrochemical reaction of the solid polymer fuel cell 100.
  • the adjacent membrane electrode assemblies 20 are electrically connected in series or in parallel to each other.
  • the peripheral portion of the separators 12 and 13 and the membrane-frame assembly 1, i.e., the frame element 6, is provided with a pair of through holes through which the fuel gas and the oxidizing gas flow, i.e., fuel gas manifold holes 16, 26, and 36 and the oxidizing gas manifold holes 17, 27, and 37.
  • the through holes accumulate to form the fuel gas manifold and the oxidizing gas manifold.
  • a fuel gas flow channel groove 24 is provided at the main surface on the inner side of the anode separator 12, so as to connect between a pair of fuel gas manifold holes 26 and 26.
  • An oxidizing gas flow channel groove 34 is formed at the main surface on the inner side of the cathode separator 13, so as to connect between a pair of oxidizing gas manifold holes 37 and 37. That is, the oxidizing gas and the fuel gas branch from their respective one manifolds, i.e., the manifolds on the supply side, to the flow channel grooves 24 and 34, and to flow into their respective other manifolds, i.e., the manifolds on the discharge side.
  • the fuel gas flow channel groove 24 has, in the state where the cell 10 is assembled, a diffusion layer abutting portion 24A formed on the front surface abutting on the diffusion layer 15 and a pair of communication portions (communication-purpose grooves) 24B formed across the front surface abutting on the diffusion layer 15 and the front surface opposing to the periphery of the diffusion layer 15.
  • the flow channel groove 34 has, in the state where the cell 10 is assembled, the diffusion layer abutting portion 34A formed on the front surface abutting on the diffusion layer 15 and a pair of communication portions (communication-purpose grooves) 34B formed across the front surface abutting on the diffusion layer 15 and the front surface opposing to the periphery of the diffusion layer 15.
  • the communication portions 24B and 34B are formed to couple a pair of manifold holes 26 and 37 and the diffusion layer abutting portions 24A and 34A, respectively.
  • the oxidizing gas and the fuel gas branch from the fuel gas manifold hole 26 and the oxidizing gas manifold hole 37 on the supply side, to flow into the communication portions 24B and 34B, respectively.
  • the oxidizing gas and the fuel gas are brought into contact with the diffusion layer 15 at the diffusion layer abutting portions 24A and 34A, respectively, to cause an electrochemical reaction.
  • the surplus gas and the reactive generation component are discharged to the fuel gas manifold hole 26 and the oxidizing gas manifold hole 37 on the discharge side via the communication portions 24B and 34B connected to the fuel gas manifold hole 26 and the oxidizing gas manifold hole 37 on the discharge side, respectively.
  • the gaskets 5 are arranged on the opposite main surfaces of the frame element 6 of the membrane electrode assembly 1.
  • the gaskets 5 are arranged such that the oxidizing gas and the fuel gas do not flow from the prescribed flow channel grooves 24 and 34. That is, the gaskets 7 are arranged to surround the periphery of the manifold holes 16, 17, and 18 and the periphery of the frame. Further, in this case, in the state where the cell 10 is assembled, the gasket 5 is not arranged on the anode separator 12 side at the position on which the communication portion 24B of the fuel gas flow channel groove 24 abuts. Further, the gasket 5 is arranged such that the fuel gas manifold hole 16 and the membrane electrode assembly 20 are integrally surrounded.
  • the gasket 5 is not arranged on the cathode separator 13 side at the position on which the communication portion 34B of the oxidizing gas flow channel groove 34 abuts. Further, the gaskets 5 prevent leakage of the fuel gas and the oxidizing gas to the outside of the fuel gas flow channel 24 and the oxidizing gas flow channel 34, such that the flow of the fuel gas flowing between the oxidizing gas manifold hole 17 and the membrane electrode assembly 20 is not inhibited, and the flow of the oxidizing gas flowing between the oxidizing gas manifold hole 37 and the membrane electrode assembly 20 is not inhibited. Note that, in Fig. 22 , for sake of convenience, the gaskets 5 and the serpentine structure of the flow channel grooves 24 and 34 of the diffusion layer abutting portions 24A and 34A of the separators 12 and 13 are shown schematically.
  • the manifolds are formed by the through holes of the separators 12 and 13.
  • external manifolds that is, manifolds formed externally to the separators 12 and 13. That is, the membrane-frame assembly 1 and the separators 12 and 13 are not provided with the fuel gas manifold holes 16, 26, and 36 and the oxidizing gas manifold holes 17, 27, and 37, and the fuel gas flow channel groove 24 and the communication portions 24B and 34B of the oxidizing gas flow channel 34 extend to end faces of the separators 12 and 13, respectively.
  • the gaskets 5 are arranged to extend to the end face of the frame element 6 along the respective peripheries of the communication portions 24B and 34B of the fuel gas flow channel groove 24 and the oxidizing gas flow channel groove 34. Note that, from the viewpoint of achieving a reduction in size of the solid polymer fuel cell 100 and a simplified appearance, it is preferable that the manifolds are formed by the through holes of the separators.
  • water gas manifold holes 18, 28, and 38 forming two pairs of manifolds, through which water flows, are provided at the peripheral portion of the separators 12 and 13 of the membrane-frame assembly 1.
  • the manifold holes are connected to one another to form the two pairs of water manifolds.
  • nonwoven fibers used for reinforcement can be efficiently produced.
  • the electrolyte membrane with high mechanical strength, excellent size stability when impregnated with water, and low resistance can be obtained.
  • the membrane electrode assembly obtained using this electrolyte membrane provides a solid polymer fuel cell with high electrical performance and high durability.

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Claims (14)

  1. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), comprenant:
    une membrane de renfort (22) faite de fibres non tissées (86); et
    un électrolyte prévu dans un espace entre les fibres non tissées (86);
    caractérisée en ce que ladite membrane d'électrolyte (2) présente une région de génération de puissance (21) et une région de cadre de joint d'étanchéité (5), ladite région de cadre de joint d'étanchéité (5) étant prévue sur toute la circonférence de la région de génération de puissance (21), les fibres non tissées (86) ayant une masse surfacique qui varie de façon continue comme un tout de ladite région de génération de puissance (21) à ladite région de cadre de joint d'étanchéité (5),
    en ce que les fibres non tissées (86) présentent une distribution massique non uniforme dans un plan de la membrane d'électrolyte (2), la masse surfacique des fibres non tissées (86) étant comprise entre 0,1 mg/cm2 et 1,5 mg/cm2, et
    en ce que les fibres non tissées (86) présentent une masse surfacique dans une région correspondant à ladite région de cadre de joint d'étanchéité (5) et une région correspondant à au moins une partie d'une portion périphérique (212) de la région correspondant à la région de cadre de joint d'étanchéité (5), qui est supérieure à une masse surfacique dans une région correspondant à une portion centrale (221) de la région de génération de puissance (21).
  2. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle une masse surfacique des fibres non tissées (86) de la région de génération de puissance (21) augmente avec une distance du centre à une zone extérieure.
  3. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 2,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans une région ayant une largeur correspondant à 10 % d'une longueur d'un côté de la région de génération de puissance (21) à partir du cadre de joint d'étanchéité (5), qui est supérieure à la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  4. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans une région (211) correspondant à une entrée de gaz combustible (3) de la pile à combustible (100) à laquelle la membrane d'électrolyte (2) est adaptable, la masse surfacique étant supérieure à la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  5. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 4,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans une région ayant une largeur correspondant à 30 % d'une longueur d'un côté (31) de la région de génération de puissance (21) pourvue de l'entrée de gaz combustible (3) de la pile à combustible à laquelle la membrane d'électrolyte (2) est adaptable, la masse surfacique étant supérieure à la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  6. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans une région (231) correspondant à une sortie de gaz combustible (4) de la pile à combustible (100) à laquelle la membrane d'électrolyte (2) est adaptable, la masse surfacique étant supérieure à la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  7. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 6,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans une région ayant une largeur correspondant à 30 % d'une longueur d'un côté (34) de la région de génération de puissance (21) pourvue de la sortie de gaz combustible (4) de la pile à combustible (100) à laquelle la membrane d'électrolyte (2) est adaptable, la masse surfacique étant supérieure à la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  8. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle les fibres non tissées (86) présentent une masse surfacique dans la région correspondant à ladite région de cadre de joint d'étanchéité (5) et la région correspondant à au moins une partie de la portion périphérique (212) de la région correspondant à la région de cadre de joint d'étanchéité (5), qui est inférieure à 15 fois la masse surfacique dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  9. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle la membrane de renfort (22) présente une épaisseur dans la région correspondant à la région de cadre de joint d'étanchéité (5) et la région correspondant à au moins une partie de la portion périphérique (212) de la région correspondant à la région de cadre de joint d'étanchéité (5), qui est supérieure à et 15 fois ou moins une épaisseur dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  10. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon la revendication 1,
    dans laquelle les fibres non tissées (86) présentent un diamètre de fibre dans la région correspondant à la région de cadre de joint d'étanchéité (5) et la région correspondant à au moins une partie de la portion périphérique (212) de la région correspondant à la région de cadre de joint d'étanchéité (5), qui est supérieur à et 15 fois ou moins un diamètre de fibre dans la région correspondant à la portion centrale (221) de la région de génération de puissance (21).
  11. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon l'une quelconque des revendications 1 à 10,
    dans laquelle les fibres non tissées (86) sont préparées par électrofilage.
  12. Membrane d'électrolyte (2) pour pile à combustible à membrane (100), selon l'une quelconque des revendications 1 à 11,
    dans laquelle l'électrolyte est une membrane échangeuse d'ions conductrice de protons.
  13. Ensemble d'électrode à membrane (20) pour pile à combustible à membrane (100), comprenant:
    la membrane d'électrolyte (2) pour pile à combustible à membrane (100) selon l'une quelconque des revendications 1 à 12; et
    un module ayant la membrane d'électrolyte (2) pour pile à combustible à membrane (100), fixée avec un joint d'étanchéité (5) et serrée entre des séparateurs.
  14. Pile à combustible à membrane, comprenant:
    au moins une pile, la pile étant construite avec ledit ensemble d'électrode à membrane (20) pour pile à combustible à membrane (100) selon la revendication 13 et une paire de séparateur d'anode et de séparateur de cathode qui serrent ledit ensemble d'électrode à membrane (20) pour pile à combustible à membrane (100).
EP11854577.1A 2011-01-07 2011-11-14 Membrane d'électrolyte pour piles à combustible à polymère solide, système d'électrode de membrane comprenant cette membrane d'électrolyte, et pile à combustible à polymère solide Active EP2642569B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011002094 2011-01-07
PCT/JP2011/006341 WO2012093432A1 (fr) 2011-01-07 2011-11-14 Membrane d'électrolyte pour piles à combustible à polymère solide, système d'électrode de membrane comprenant cette membrane d'électrolyte, et pile à combustible à polymère solide

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EP2642569A1 EP2642569A1 (fr) 2013-09-25
EP2642569A4 EP2642569A4 (fr) 2013-12-18
EP2642569B1 true EP2642569B1 (fr) 2015-03-25

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JPWO2012093432A1 (ja) 2014-06-09
WO2012093432A1 (fr) 2012-07-12
JP5193394B2 (ja) 2013-05-08
US9419301B2 (en) 2016-08-16
EP2642569A1 (fr) 2013-09-25
US20130273455A1 (en) 2013-10-17
EP2642569A4 (fr) 2013-12-18

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